TWI725700B - Poly(amide-imide) copolymer, composition and polymer film comprising thereof and method for producing polymer film - Google Patents

Abstract

The present disclosure relates to a poly(amide-imide) copolymer in which at least one of an imide repeating unit and an amide repeating unit is substituted with a specific functional group, a composition and a polymer film comprising the same and a method for producing a polymer film.

Description

Polyamide-imine copolymer, its composition and polyamide Composite film and method for producing polymer film

The present disclosure relates to a polyamide-imine copolymer, a composition containing the same and a polymer film, and a method for producing the polymer film.

[Cross reference of related applications]

This application claims the Korean patent application No. 10-2019-0003997 filed with the Korean Intellectual Property Office on January 11, 2019, and the Korean patent application filed with the Korean Intellectual Property Office on January 8, 2020 The priority or right of No. 10-2020-0002769, and the disclosure content of the Korean patent application is incorporated into this case for reference in its entirety.

Polyimide resin is a polymer with relatively low crystallinity or mainly an amorphous structure, and exhibits excellent heat resistance, chemical resistance, electrical properties, and dimensional stability due to its rigid chain structure. Therefore, these polyimide resins are widely used as materials for electrical/electronic devices.

However, polyimine resins have many limitations in their use. This is because these polyimine resins can be affected by the charge transfer complex (CTC) of π electrons present in the imine chain. It forms and appears dark brown.

In order to solve the above limitation and obtain a colorless and transparent polyimide resin, the following method has been proposed: by introducing a strong electron attracting group (for example, trifluoromethyl (-CF ₃ )), the movement of π electrons is carried out. The method of restriction, the method of _{reducing the formation of charge transfer complexes by introducing sulfonyl group (-SO 2} -), ether group (-O-), etc. into the main chain to form a curved structure; or by introducing fat It is a method of suppressing the formation of a π-electron resonance structure with a cyclic compound.

However, it is difficult for the polyimide resin proposed above to exhibit sufficient heat resistance due to a curved structure or aliphatic cyclic compound, and the film prepared using the polyimide resin still has, for example, poor mechanical properties, etc. limit.

In addition, most polyimide resins are formed by imidizing polyimide as a precursor, but because the final curing is performed in a curing process at a high temperature of 300°C or higher Therefore, the physical properties of wires and substrates are reduced, especially when used as semiconductor protective films, which can cause problems such as reducing the electrical properties of semiconductors or destroying the properties of semiconductors.

Therefore, in order to be used as a flexible display material in recent years, it is necessary to develop a polyamide-imide copolymer that can be cured at a low temperature and has excellent optical properties, mechanical properties, and chemical resistance.

The purpose of the present disclosure is to provide a polyamide-imide copolymer that can be cured at a low temperature, is colorless and transparent, and also exhibits excellent mechanical properties, heat resistance, and chemical resistance.

Another objective of the present disclosure is to provide a composition and polymer film comprising polyamide-imide copolymer.

In one aspect of the present disclosure, a polyamide-amide copolymer can be provided, in which at least one of the amide repeat unit and the amide repeat unit is substituted with one or more specific functional groups.

In another aspect of the present disclosure, a composition including a polyamide-imine copolymer can be provided.

In another aspect of the present disclosure, a polymer film containing a polyamide-imide copolymer can be provided.

Hereinafter, the polyamide-imine copolymer, the composition containing the same, and the polymer film according to the embodiments of the present disclosure will be described in more detail.

Unless explicitly stated herein, these terms are only used to describe specific exemplary embodiments, and are not intended to limit the present disclosure.

Unless the phrase clearly expresses the opposite meaning, the singular term used in this article includes the plural term.

It should be understood that the terms "including", "including" and the like used herein are intended to specifically describe certain features, regions, integers, steps, operations, elements, and/or components, and these do not The possibility of the existence or addition of other features, integers, steps, operations, elements, components, and/or groups is not excluded.

(Meth)acrylic acid as used herein is intended to include both acrylic acid and methacrylic acid.

As used herein, "*" means a position connected to the same or different atom or chemical formula.

The amide repeating unit used herein means a repeating unit having an amide bond in the polymer main chain, and an amide repeating unit means a repeating unit having an amide bond in the polymer main chain.

According to an embodiment of the present disclosure, a polyamide-imidine copolymer can be provided, wherein at least one of the amide repeating unit and the amide repeating unit is substituted with one or more functional groups including the following chemical formula 1 .

Wherein, R ₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and L is a single bond or an alkylene group having 1 to 10 carbon atoms.

The inventors have discovered through experiments that when at least one of the amide repeating unit and the amide repeating unit included in the polyamide-imid copolymer includes a functional group including Chemical Formula 1, it can be 200℃ or below 200℃ or 150℃ or below It is cured at a low temperature of 150°C, and while being colorless and transparent, it also exhibits excellent mechanical properties, heat resistance and chemical resistance, thus completing the present disclosure.

Therefore, polyamide-imine copolymers can be effectively used in products or industrial fields that require low-temperature curing while requiring high mechanical properties, for example, as display substrates, protective polymer films for displays, touch panels, Flexible or foldable device covering polymer film.

The polyamide-imine copolymer of this embodiment includes an amide repeating unit having an amide bond in the polymer main chain and an amide repeating unit having an amide bond in the polymer main chain, wherein At least one of the imine repeat unit and the amide repeat unit may be substituted with one or more functional groups including Chemical Formula 1.

Based on 100 mole parts of the polyamide-imine copolymer, the repeating unit in which one or more functional groups of Chemical Formula 1 is substituted may be included in an amount of 5 mole parts to 100 mole parts. When the content of the substituted repeating unit including one or more functional groups of Chemical Formula 1 is less than 5 mol parts, the degree of ultraviolet (UV) curing becomes extremely low, and it becomes difficult to intervene in the polymer chain. Fully cross-linked between.

Hereinafter, the above-mentioned polyamide-imine copolymer will be explained in more detail.

Since the polyamide-imidine copolymer together includes an amide repeating unit and an amide repeating unit, and at least one of the amide repeating unit and the amide repeating unit is substituted with a photocurable functional group including chemical formula 1. , So it can be cured by light, and at the same time improve the thermal, mechanical and optical properties of the copolymer. Therefore, in the subsequent polymer film manufacturing process, the thermal curing process can be at 200°C or lower than 200°C or 150°C. Or at a low temperature of less than 150℃, and can prevent the wires and substrates, especially It is the problem of deterioration of the physical properties of the wafer.

Specifically, in the functional group including Chemical Formula 1, R ₁ may be hydrogen or methyl.

In addition, L may be an alkylene group having 1 to 5 carbon atoms, and may also be an ethylene group.

In addition, the functional group including Chemical Formula 1 may be any one selected from the group consisting of:

(i) The imine repeating unit: the first repeating unit and the second repeating unit

The repeating unit of the imine included in the polyimide-imine copolymer according to one embodiment may include a first repeating unit represented by the following chemical formula 2-1 and a second repeating unit represented by the following chemical formula 2-2 Anyone in's groups.

[Chemical formula 2-1]

p

10)、-(CF₂)q-(其中1

q

10)、-C(CH₃)₂-、-C(CF₃)₂-或-C(=O)NH-，且a、b及c各自獨立地為1至4的整數。 Wherein, in Chemical Formula 2-1 and Chemical Formula 2-2, X ₁ is a tetravalent organic group, and R ₂ to R ₄ are each independently hydrogen; a hydroxyl group; an alkyl group having 1 to 10 carbon atoms; or including the chemical formula 1. The functional group of Q ₁ is a single bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) _2- , -(CH ₂ )p-(where 1

p

10), -(CF ₂ )q-(where 1

q

10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -or -C(=0)NH-, and a, b, and c are each independently an integer of 1 to 4.

For example, the X ₁ may be any one selected from the group represented by the following structural formulas.

In addition, in Chemical Formula 2-1, R ₂ may be a functional group including Chemical Formula 1.

In addition, in Chemical Formula 2-2, _{at least one of R 3} and R ₄ may be a functional group including Chemical Formula 1.

In addition, the molar ratio of the first repeating unit to the second repeating unit in the polyamide-imine copolymer may be 10:90 to 90:10, 20:80 to 80:20, or 30:70 to 70: 30. By satisfying these molar ratios, the copolymer is colorless and transparent, and can exhibit excellent heat resistance and chemical resistance while maintaining high mechanical properties. At the same time, when the molar ratio of the first repeating unit to the second repeating unit is outside the above range, problems such as yellowing may occur.

(ii) Amide repeating unit: the third repeating unit and the fourth repeating unit

The amide repeating unit included in the polyamide-imid copolymer according to an embodiment may include a third repeating unit represented by the following chemical formula 3-1 and a fourth repeating unit represented by the following chemical formula 3-2 Anyone in the group.

p

10)、-(CF₂)q-(其中1

q

10)、-C(CH₃)₂-、-C(CF₃)₂-或-C(=O)NH-，且d、e及f各自獨立地為1至4的整數。 Wherein, in Chemical Formula 3-1 and Chemical Formula 3-2, X ₂ is an aryl group having 6 to 30 carbon atoms, and R ₅ and R ₆ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms , R ₇ to R ₉ are each independently hydrogen; a hydroxyl group; an alkyl group having 1 to 10 carbon atoms; or a functional group including chemical formula 1, Q ₂ is a single bond, -O-, -S-, -C( =O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ )p- (where 1

p

10), -(CF ₂ )q-(where 1

q

10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -or -C(=0)NH-, and d, e, and f are each independently an integer of 1 to 4.

For example, the X ₂ may be any one selected from the group represented by the following structural formulas.

In addition, in Chemical Formula 3-1, R ₇ may be a functional group including Chemical Formula 1.

In addition, in Chemical Formula 3-2, _{at least one of R 8} and R ₉ may be a functional group including Chemical Formula 1.

In addition, the molar ratio of the third repeating unit to the fourth repeating unit in the polyamide-imine copolymer may be 10:90 to 90:10 or 10:90 to 50:50. By satisfying these molar ratios, the copolymer is colorless and transparent, and can exhibit excellent heat resistance and chemical resistance while maintaining high mechanical properties. At the same time, when the molar ratio of the third repeating unit to the fourth repeating unit is outside the above range, problems such as increased haze or yellowing may occur.

The molar ratio of the amide repeating unit to the amide repeating unit included in the polyamide-imid copolymer according to an embodiment may be 10:90 to 90:10, 20:80 to 80:20 or 30 : 70 to 70:30. If such a molar ratio is outside the above range, problems such as increased haze or decreased solubility may occur.

At the same time, the weight average molecular weight of the polyamide-imine copolymer may be 5,000 g/mol to 300,000 g/mol, 10,000 g/mol to 250,000 g/mol or 50,000 g/mole to 200,000 g/mole. If the weight average molecular weight of the polyamide-imine copolymer is less than 5,000 g/mole, it may be difficult to form a film with the composition containing the copolymer, and if it exceeds 300,000 g/mole, there is a decrease in solubility The problem. In this specification, the weight average molecular weight means the weight average molecular weight in terms of polystyrene measured by Gel Permeation Chromatography (GPC).

According to another embodiment of the present disclosure, a composition including a polyamide-imine copolymer is provided.

The composition includes a polyamide-imide copolymer having excellent transparency, heat resistance, chemical resistance, and mechanical strength as described above, thereby providing a polyamide-imide copolymer capable of forming excellent transparency, heat resistance, chemical resistance, and The composition of the mechanically strong polymer film.

In addition, since the polyamide-imine copolymer is substituted with a functional group including chemical formula 1 capable of photocuring, the copolymer can be thermally cured at a low temperature, thereby preventing the physical properties of wires or substrates, especially wafers. The problem of deterioration.

In addition to the polyamide-imine copolymer, the composition may further include a photoinitiator, a multifunctional (meth)acrylate monomer, a solvent, and the like.

As the multifunctional (meth)acrylate monomer, mention may be made of difunctional acrylates, such as 1,2-ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate , 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate Base) acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, dicyclopentyl di(meth)acrylate or hexyl Lactone-modified dicyclopentene di(meth)acrylate; trifunctional acrylate, such as trimethylolpropane tri(meth)acrylate or dipentaerythritol tri(meth)acrylate; tetrafunctional acrylate , Such as diglyceride tetra(meth)acrylate or pentaerythritol tetra(meth)acrylate; five-functional acrylate, such as propionic acid-modified dipentaerythritol penta(meth)acrylate; and hexafunctional acrylate, such as two Pentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate modified by caprolactone, or urethane (meth)acrylate, but not limited thereto. In addition, as specific examples, Kayarad DPCA-20, Kayarad DPCA-30, Kayarad DPCA-60, Kayarad DPCA120, Kayarad DPEA-12, Kayarad DPCA-20, One or more of Yarad HX-620, etc. (manufactured by Nippon Kayaku Co., Ltd.), but not limited thereto.

The photoinitiator that may be additionally included in the composition may include, for example, α-hydroxy ketone compounds (for example, IRGACURE 184, IRGACURE 500, IRGACURE 2959, DAROCUR 1173; Ciba Specialty Chemicals (manufactured by Ciba Specialty Chemicals): phenylglyoxylic acid compounds (e.g. Yanjiagou 754, Darokal MBF; manufactured by Ciba Specialty Chemicals); benzyl dimethyl ketal compounds (e.g Yanjiagu 651; manufactured by Ciba Special Chemicals Co., Ltd.); α-amino ketone compounds (such as Yanjiagu 369, Yanjiagu 907, and Yanjiagu 1300; manufactured by Ciba Special Chemicals Company); Phosphine compounds (MAPO) (for example, Darokal TPO; manufactured by Ciba Specialty Chemicals); bis-aminophosphine compounds (BAPO) (for example, Yanjiagou 819, Yanjiagou 819DW; by Ciba Specialty Chemicals Manufactured by the company); phosphine oxide compounds (for example, Yanjiagu 2100: manufactured by Ciba Specialty Chemicals); Maojin Genus compounds (for example, Yanjia solid 784; manufactured by Ciba Special Chemicals Company); iodonium salts (such as Yanjia solid 250; manufactured by Ciba Special Chemicals Company); Carl 4265, Yanjiagou 2022, Yanjiagou 1300, Yanjiagou 2005, Yanjiagou 2010, Yanjiagou 2020; manufactured by Ciba Specialty Chemicals Co., Ltd.), but not limited to these.

Based on 100 parts by weight of the polyamide-imine copolymer, the photoinitiator may be included in an amount of 0.1 to 10 parts by weight and 0.5 to 8 parts by weight. If the content of the photoinitiator is less than 0.5 parts by weight, the polymer film containing the polyamide-imine copolymer cannot be sufficiently cured. If the content exceeds 8 parts by weight, the optical properties and mechanical properties of the polymer film may be deteriorated.

The composition according to other embodiments may further include a surfactant. Based on 100 parts by weight of polyimide, the surfactant may be included in an amount of 0.001 parts by weight to 0.8 parts by weight. If the content of the surfactant is less than 0.001 parts by weight, the surface of the polymer film containing the polyamide-imide copolymer cannot be uniformly formed, and if it exceeds 0.8 parts by weight, the composition becomes difficult to cure and mechanically The properties can be reduced.

The composition according to other embodiments may further include a solvent for controlling viscosity. The solvent may include, for example, tetrahydrofuran (THF), propylene glycol monoethyl ether (PGMEA), methyl ethyl ketone (MEK), dimethylacetamide (DMAc), etc., but is not limited thereto.

Based on 100 parts by weight of the polyamide-imine copolymer, the solvent may be included in an amount of 50 parts by weight to 1000 parts by weight. If the content of the solvent is less than 50 parts by weight, Then there is the problem of reduced solubility. If the content exceeds 1000 parts by weight, the viscosity may be too low, and it may be difficult to coat a composition containing a polyamide-imine copolymer.

According to another embodiment of the present disclosure, a polymer film including a polyamide-imine copolymer is provided.

The polymer film includes the polyamide-imine copolymer having excellent transparency, heat resistance, chemical resistance and mechanical strength as described above, thereby providing excellent transparency, heat resistance, chemical resistance and mechanical strength. Strong polymer film.

Specifically, according to American Society For Testing And Materials (ASTM) D1925 based on a thickness measurement of 50±2 microns, a polymer film containing a polyamide-imide copolymer may have a thickness of 3.0 Or a yellow index (YI) less than 3.0, 2.5 or less than 2.5 or 2.0 or less than 2.0. When the yellow index of the polymer film is within the above range, it can appear transparent and colorless.

In addition, when measured by ASTM D1003, the polymer film containing the polyamide-imide copolymer may have a haze of 2% or less than 2%, 1.5% or less than 1.5%, or 1.0% or less than 1.0%. When the haze of the polymer film is within the range, the polymer film may be sufficiently transparent and thus has excellent clarity.

The polymer film may have a thickness of 20 micrometers to 100 micrometers, 30 micrometers to 90 micrometers, or 40 micrometers to 80 micrometers, but is not limited thereto. The thickness can be adjusted appropriately according to the application.

According to another embodiment of the present disclosure, there is provided a method for producing a polymer film. The method includes the following steps: coating on a substrate and heating at 200°C or lower Cured at a temperature of 200°C.

Specifically, the method of producing a polymer film may include the following steps: coating a composition including a polyamide-imide copolymer on a substrate, and curing the coated composition.

In addition, the step of curing the coated composition may include both photocuring and thermal curing. Such light curing and thermal curing can be performed simultaneously or sequentially. For example, photocuring may be performed to semi-cure the coated composition, and then thermally cured at a low temperature to finally produce a polymer film.

In particular, the polyamide-imine copolymer can be photocured by including a photocurable functional group including Chemical Formula 1.

During such a photo-curing step, the irradiation dose of ultraviolet light may be, for example, about 200 mJ/cm² to about 1500 mJ/cm². As a light source for ultraviolet irradiation, for example, a high-pressure mercury lamp, a metal halide lamp, a black fluorescent lamp, etc. can be used, but it is not limited thereto. The photocuring step can be performed by irradiating with the irradiation dose as described above for about 1 minute to 10 minutes.

Since the polyamide-imine copolymer can be photocured, it can even be thermally cured at a low temperature of 200°C or lower or 90°C to 180°C. In addition, by additionally performing such low-temperature thermal curing, the physical properties of the polymer film can be improved. If the temperature exceeds 200°C, the physical properties of the film may be reduced.

Meanwhile, specific examples of the substrate include various plastic polymer films or glass substrates, such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, and cellulose diacetate. Plain, poly(meth)acrylate alkyl ester, Poly(meth)acrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride. Vinyl acetate copolymer, polytetrafluoroethylene and polytrifluoroethylene, but not limited thereto.

At the same time, for example, as the coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a micro-gravure coating method, a comma coating method, a slit die coating method can be used , Lip coating method, solution casting method, etc., but not limited to this.

Since polymer films exhibit excellent transparency, heat resistance, chemical resistance, and mechanical strength, they can be used in a variety of fields, such as device substrates, display substrates, optical polymer films, and integrated circuits (IC). ) Encapsulation, bonding polymer film, multilayer frame rate control (Frame Rate Control, FRC) (flexible printed circuit), tape, touch panel, protective polymer film for optical discs, etc.

According to the present disclosure, there is provided a polyamide-imide copolymer that is colorless and transparent, has excellent mechanical properties, heat resistance, and chemical resistance, and can be cured at a low temperature, and a composition and polymer film containing the same.

Since the polymer film containing the polyamide-imide copolymer has the above-mentioned characteristics, it can be applied to display substrates, protective polymer films for displays, touch panels, flexible or foldable devices Cover polymer film etc.

Hereinafter, preferred examples are provided for better understanding. However, these examples are only for illustrative purposes, and the present disclosure is not intended to be limited by these examples.

[Examples and Comparative Examples: Preparation of Copolymers]

Example 1: Preparation of polyamide-imine copolymer (A)

To a 500 ml three-necked round bottom flask equipped with a Dean-Stark trap, nitrogen inlet and mechanical stirrer, 6.34 g (19.8 millimoles) of 2,2'-double (Trifluoromethyl)-4,4'-diaminobiphenyl (TFMB) and 3.63 g (9.91 mmol) 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane ( BisAPAF), while passing nitrogen through it, dissolved in 183 g of N-methyl-2-pyrrolidone (NMP), and then heated at 40°C.

Then, 8.00 g (18.0 millimoles) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 6FDA) was added to it, and The mixture was stirred at 40°C for about 3 hours. 2.44 grams (12.0 millimoles) terephthaloyl chloride (terephthaloyl chloride, TPC), and then stirred for 3 hours.

Then, 0.47 g (3.00 mmol) of γ-valerolactone, 0.47 g (5.94 mmol) of pyridine, and 20 g of toluene were added, and then stirred at 150°C for 24 hours. After the reaction was completed, an excessive amount of ethanol (2 liters) was added dropwise to the stirred reaction solution to form a precipitate. The obtained precipitate was separated by filtration under reduced pressure, washed three times with ethanol, and then dried under vacuum at room temperature for about 24 hours to obtain 15 g of intermediate (A-1).

Add 15 grams of intermediate (A-1) and 0.3 grams (1.36 millimoles) of butylated hydroxy toluene (BHT) to a 500 ml three-necked round bottom flask, while allowing nitrogen to pass through and dissolve In 200 grams of tetrahydrofuran (THF).

1.56 grams (10.1 millimoles) of 2-(methacryloyloxy) ethyl isocyanate (MOI) and 0.38 grams (0.60 millimoles) of dibutyltin dilaurate were added sequentially , Heated at 50 ℃, and then stirred for 18 hours. After the reaction was completed, an excessive amount of ethanol (2 liters) was added dropwise to the stirred reaction solution to form a precipitate. The precipitate obtained was separated by filtration under reduced pressure, washed with ethanol three times, and then dried under vacuum at room temperature for about 24 hours to obtain 12 g of polyamide-imine copolymer (A) .

The molecular weight of the obtained polyamide-imine copolymer (A) was measured by gel permeation chromatography (GPC) in THF solvent, and the measurement result showed that the weight average molecular weight (Mw) was 48,000 g /Mole.

Example 2: Preparation of polyamide-imine copolymer (B)

Except for the use of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl and 2,2 in amounts of 7.69 g (24.0 millimoles) and 2.20 grams (6.00 millimoles), respectively Except for bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 12.2 g of polyamide-imine copolymer (B) was prepared in the same manner as in Example 1.

The molecular weight of the obtained polyamide-imine copolymer (B) was measured by gel permeation chromatography (GPC) in THF solvent, and the measurement result showed that the weight average molecular weight (Mw) was 46,000 g /Mole.

Example 3: Preparation of polyamide-imine copolymer (C)

Except that 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl and 2,2 are used in amounts of 5.76 g (18.0 millimoles) and 4.40 grams (12.00 millimoles) respectively. Except for bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 12.2 g of polyamide-imine copolymer (C) was prepared in the same manner as in Example 1.

The molecular weight of the obtained polyamide-imine copolymer (C) was measured by gel permeation chromatography (GPC) in THF solvent, and the measurement results showed that the weight was equal The average molecular weight (Mw) is 52,000 g/mol.

Example 4: Preparation of polyamide-imine copolymer (D)

Except for the use of 4,4'-(hexafluoroisopropyl)diphthalic anhydride and terephthalic anhydride in amounts of 9.33 g (21.0 millimoles) and 1.83 grams (9.0 millimoles), respectively. In addition, 12 g of polyamide-imine copolymer (D) was prepared in the same manner as in Example 1.

The molecular weight of the obtained polyamide-imine copolymer (D) was measured by gel permeation chromatography (GPC) in THF solvent, and the measurement result showed that the weight average molecular weight (Mw) was 41,000 g /Mole.

Comparative Example 1: Preparation of polyimide (E)

To a 500 ml three-neck round bottom flask equipped with a Dean-Stark trap, nitrogen inlet and mechanical stirrer, 6.34 g (19.8 mmol) of 2,2'-bis(trifluoromethyl) )-4,4'-diaminobiphenyl (TFMB) and 3.63 grams (9.91 millimoles) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BisAPAF), at the same time Nitrogen from Pass, dissolve in 183 grams of N-methyl-2-pyrrolidone (NMP), and then heat at 40°C.

Then, 8.88 g (20.0 millimoles) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added thereto, and the mixture was stirred at 40°C for about 4 hours.

Then, 1.39 g (6.31 mmol) of butylated hydroxytoluene (BHT), 23.7 g (300 mmol) of pyridine, and 23.1 g (150 mmol) of methacrylic anhydride were stirred at 60°C overnight. After the reaction was completed, an excessive amount of ethanol (2 liters) was added dropwise to the stirred reaction solution to form a precipitate. The precipitate obtained was separated by filtration under reduced pressure, washed with ethanol three times, and dried in a vacuum oven at 80°C for about 8 hours to obtain 12 g of polyimide having a methacrylate group Resin (E).

Comparative Example 2: Preparation of polyamide-imine copolymer (F)

To a 500 ml three-necked round bottom flask equipped with a Dean-Stark trap, nitrogen inlet and mechanical stirrer, 9.51 g (29.7 mmol) of 2,2'-bis(trifluoromethyl) )-4,4'-diaminobiphenyl (TFMB), while passing nitrogen through it, dissolved in 183 g of N-methyl-2-pyrrolidone (NMP), and then heated at 40°C.

Then, 8.00 grams (18.0 millimoles) of 4,4'-(hexafluoro Isopropyl)diphthalic anhydride (6FDA), and the mixture was stirred at 40°C for about 4 hours. 2.44 g (12.0 millimoles) of terephthalic acid chloride (TPC) was added thereto, followed by stirring for 3 hours.

Then, the temperature was raised to 200°C, and the reaction was further carried out for 15 hours. After the reaction was completed, an excessive amount of ethanol (2 liters) was added dropwise to the stirred reaction solution to form a precipitate. The precipitate obtained was separated by filtration under reduced pressure, washed three times with ethanol, and dried in a vacuum oven at 80°C for about 8 hours to obtain 12 g of polyamide-imine copolymer (F ).

Comparative Example 3: Preparation of polyamide-imine copolymer (G)

Under nitrogen flow, 350 grams of N,N-dimethylacetamide (DMAc) was charged into the reactor, and then 21.0 grams (65.6 millimoles) of 2,2' -Bis(trifluoromethyl)-4,4'-biphenyldiamine (TFMB) dissolves. 17.7 g (39.8 millimoles) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added to the TFMB solution at the same temperature and dissolved for a predetermined time under stirring.

After thorough stirring, the temperature was lowered to 0°C, 5.38 g (26.5 mmol) of terephthalic acid chloride (TPC) was added thereto, and stirring was continued. The viscosity of the polyamide-imine precursor solution produced by the reaction is adjusted to a predetermined level to obtain a polyamide-imine precursor solution with a solid content of 13%. 3.46 g (43.7 mol) of pyridine and 4.46 g (43.7 mol) of acetic anhydride were added to the solution, stirred well, and then precipitated with methanol. The precipitated solid was filtered and dried in a vacuum oven at 100°C for 24 hours to obtain a polyamide-imide solid.

Dissolve the dried polyamide-imine in 300 grams of DMAc, and add to it Added 2 moles of 2-(methacryloxy) ethyl isocyanate (MOI) and 50 grams of DMAc. The resulting solution was reacted at 50°C for 6 hours, and then precipitated with methanol. The precipitated solid was dried to obtain a polyamide-imine copolymer (G).

Comparative Example 4: Preparation of polyamide-imine copolymer (H)

Under nitrogen flow, 350 grams of N,N-dimethylacetamide (DMAc) was charged into the reactor, and then 21.0 grams (65.6 millimoles) of 2,2' -Bis(trifluoromethyl)-4,4'-biphenyldiamine (TFMB) dissolves. At the same temperature, 20.6 g (46.4 millimoles) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added to the TFMB solution and dissolved for a predetermined time under stirring.

After thorough stirring, the temperature was lowered to 0°C, 4.04 g (19.9 mmol) of terephthalic acid chloride (TPC) was added thereto, and stirring was continued. The viscosity of the polyamide-imine precursor solution produced by the reaction is adjusted to a predetermined level to obtain a polyamide-imine precursor solution with a solid content of 13%. 4.19 g (53.0 mol) of pyridine and 5.41 g (53.0 mol) of acetic anhydride were added to the solution, stirred well, and then precipitated with methanol. The precipitated solid was filtered and dried in a vacuum oven at 100°C for 24 hours to obtain a polyamide-imide solid.

The dried polyamide-imine was dissolved in 300 g of DMAc, and 2 moles of 2-(methacryloxy) ethyl isocyanate (MOI) and 50 g of DMAc were added thereto. The resulting solution was reacted at 50°C for 6 hours, and then precipitated with methanol. The precipitated solid was dried to obtain a polyamide-imine copolymer (H).

Comparative Example 5: Preparation of polyamide-imine copolymer (I)

Load 350 grams of N,N-dimethylacetamide (DMAc) under nitrogen flow In the reactor, 21.0 g (65.6 mmol) of 2,2'-bis(trifluoromethyl)-4,4'-benzidine (TFMB) Dissolve. After thorough stirring, the temperature was lowered to 0°C, 4.04 g (19.9 mmol) of terephthalic acid chloride (TPC) was added thereto, and stirring was continued. At the same temperature, 20.6 g (46.49 millimoles) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) was added to the TFMB solution and dissolved for a predetermined time under stirring .

After thorough stirring, the temperature was lowered to 0°C, 4.04 g (19.9 mmol) of terephthalic acid chloride (TPC) was added thereto, and stirring was continued. The viscosity of the polyamide-imine precursor solution produced by the reaction is adjusted to a predetermined level to obtain a polyamide-imine precursor solution with a solid content of 13%. 3.14 g (39.8 mol) of pyridine and 4.06 g (39.8 mol) of acetic anhydride were added to the solution, stirred well, and then precipitated with methanol. The precipitated solid was filtered and dried in a vacuum oven at 100°C for 24 hours to obtain a polyamide-imide solid.

The dried polyamide-imine was dissolved in 300 g of DMAc, and 2 moles of 2-(methacryloxy) ethyl isocyanate (MOI) and 50 g of DMAc were added thereto. The resulting solution was reacted at 50°C for 6 hours, and then precipitated with methanol. The precipitated solid was dried to obtain polyamide-imine copolymer (I).

Comparative Example 6: Preparation of polyamide-imine copolymer (K)

Under nitrogen flow, 350 grams of N,N-dimethylacetamide (DMAc) was charged into the reactor, and then 21.0 grams (65.6 millimoles) of 2,2' -Bis(trifluoromethyl)-4,4'-biphenyldiamine (TFMB) dissolves. 20.6 g (46.4 millimoles) 4,4'-(hexafluoroisopropylidene) diphthalic acid at the same temperature Anhydride (6FDA) was added to the TFMB solution and dissolved for a predetermined time under stirring.

After thorough stirring, the temperature was lowered to 0°C, 4.04 g (19.9 mmol) of terephthalic acid chloride (TPC) was added thereto, and stirring was continued. The viscosity of the polyamide-imine precursor solution produced by the reaction is adjusted to a predetermined level to obtain a polyamide-imine precursor solution with a solid content of 13%. 3.46 g (43.7 mol) of pyridine and 4.46 g (43.7 mol) of acetic anhydride were added to the solution, stirred well, and then precipitated with methanol. The precipitated solid was filtered and dried in a vacuum oven at 100°C for 24 hours to obtain a polyamide-imide solid.

The dried polyamide-imine was dissolved in 300 g of DMAc, and then 2 moles of 2-(methacryloxy)ethyl isocyanate (MOI) and 50 g of DMAc were added thereto. The resulting solution was reacted at 50°C for 6 hours, and then precipitated with methanol. The precipitated solid was dried to obtain a polyamide-imine copolymer (K).

Experimental example

The polyamide-imide or polyamide resin obtained in the examples and comparative examples and the DPCA-120 monomer (multifunctional (meth)acrylate monomer) were mixed in a weight ratio of 5:1 and dissolved In methyl ethyl ketone (MEK), it becomes 20% by weight solids with 2% by weight of Yanjiagu 184 starter. The mixed solution thus obtained was coated on a glass substrate by a doctor blade coating method, dried at 60°C for 5 minutes, and photocured using an ultraviolet curing machine. Then, the resultant was heat-treated at 120°C for 10 minutes, and peeled off to obtain a polyimide film. Then, the polyimide film was evaluated for physical properties by the following methods, and the results are shown in Table 1 below.

Experimental example 1: Yellow index (Y.I.)

According to the measurement method defined in ASTM D1925, the COH-400 spectrophotometer (NIPPON DENSHOKU INDUSTRIES) was used to measure the yellow index of the film sample (thickness of 50±2 microns), and the results are shown in In Table 1 below.

Experimental example 2: Glass transition temperature (Tg)

The glass transition temperature of the thin film sample (thickness of 50±2 microns) was measured using a TMA IC600 device, and its value is shown in Table 1 below.

Experimental example 3: Modulus

The modulus (modulus, billion Pa) of the film sample (thickness of 50±2 microns) was measured using DMA q800, and the results are shown in Table 1.

According to Table 1, it was confirmed that in Examples 1 to 4, the yellow index was low, and both the glass transition temperature and the modulus were high. On the other hand, it was confirmed that Comparative Example 1 had a problem of low modulus, and Comparative Examples 2 to 6 had problems of high yellow index and low glass transition temperature and modulus.

Although the present invention has been described in conjunction with exemplary embodiments that are currently considered practical, it should be understood that the present invention is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and equivalent arrangements included in the spirit and scope of the appended patent application.

Claims (15)

A polyamide-imine copolymer, wherein at least one of the amide repeating unit and at least one of the amide repeating unit is substituted with one or more functional groups including the following chemical formula 1:

Wherein, R ₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and L is a single bond or an alkylene group having 1 to 10 carbon atoms. The polyamide-imine copolymer according to claim 1, wherein R ₁ is hydrogen or methyl. The polyamide-imine copolymer according to claim 1, wherein L is an alkylene group having 1 to 5 carbon atoms. The polyimide-imine copolymer according to claim 1, wherein the repeating unit of the imine comprises a first repeating unit represented by the following chemical formula 2-1 and a second repeating represented by the following chemical formula 2-2 Any one of the group consisting of units: [Chemical formula 2-1]

Wherein, in Chemical Formula 2-1 and Chemical Formula 2-2, X ₁ is a tetravalent organic group, and R ₂ to R ₄ are each independently hydrogen; a hydroxyl group; an alkyl group having 1 to 10 carbon atoms; or including the chemical formula 1. The functional group of Q ₁ is a single bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) _2- , -(CH ₂ )p-(where 1

p

10), -(CF ₂ )q-(where 1

q

10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -or -C(=0)NH-, and a, b, and c are each independently an integer of 1 to 4. The polyamide-imine copolymer according to claim 1, wherein the repeating unit of the amide comprises a third repeating unit represented by the following chemical formula 3-1 and a fourth repeating unit represented by the following chemical formula 3-2 Any one of the group:

Wherein, in Chemical Formula 3-1 and Chemical Formula 3-2, X ₂ is an aryl group having 6 to 30 carbon atoms, and R ₅ and R ₆ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms , R ₇ to R ₉ are each independently hydrogen; a hydroxyl group; an alkyl group having 1 to 10 carbon atoms; or a functional group including chemical formula 1, Q ₂ is a single bond, -O-, -S-, -C( =O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ )p- (where 1

p

10), -(CF ₂ )q-(where 1

q

10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -or -C(=O)NH-, d, e and f are each independently an integer of 1 to 4. The polyamide-imine copolymer according to claim 4, wherein the X ₁ is any one selected from the group represented by the following structural formulas:

The polyamide-imine copolymer according to claim 5, wherein the X ₂ is any one selected from the group represented by the following structural formulas:

The polyamide-imine copolymer according to claim 1, wherein the molar ratio of the amide repeating unit to the amide repeating unit is 10:90 to 90:10. The polyamide-imine copolymer according to claim 1, wherein the weight average molecular weight of the polyamide-imine copolymer is 5,000 g/mol Ear to 300,000 g/mol. A composition comprising the polyamide-imine copolymer according to claim 1. The composition according to claim 10 further contains a photoinitiator. The composition according to claim 10, wherein the composition further comprises a multifunctional (meth)acrylate monomer. A polymer film comprising the polyamide-imine copolymer according to claim 1. The polymer film according to claim 13, wherein the yellow index measured according to the American Society for Testing and Materials D1925 based on a thickness of 50±2 microns is 3.0 or less, and the haze measured according to the American Society for Testing and Materials D1003 It is 2% or less than 2%. A method for producing a polymer film, comprising the following steps: coating a composition containing the polyamide-imine copolymer as described in claim 1 on a substrate, and at a temperature of 200°C or lower The coated composition is cured down.